Plastic material and method of producing the same



Patented Nov. 1 6, 1937 UNITED STATES PATENT OFFICE PLASTIC MATERIAL ANDMETHOD OF PRO- DUCING THE SAME No Drawing. Application December 30,1933, Se-

rial No. 704,754. In Germany December 31,

19 Claims.

The present invention relates to the manufacture of rubber and otherplastic material and more particularly to the introduction of variousingredients such, for example, as coloring matter, ae-

t; celerators and other material introduced for load ing or for otherpurposes.

The invention has for an object to provide an effective method ofdistributing the addition materials throughout the plastic mass and toproduce a product of uniformity of composition and of high quality.

, The invention has been developed more particularly in connection withthe production of vul canized rubber having incorporated thereinaccelerators of various types together with coloring matter and otherloading material and involves features more particularly applicable torubber compounds. The invention, however, is not limited to rubbermixtures but may be applied to various other plastic mixtures especiallythose in so The alcohols or their derivatives may either be mixed withthe addition material, such as carbon I black or other coloring orloading matter, accelerators, anti-aging agents or other additionmaterials and especially the dusty or granular components and thenthismixture added to the rubber or other base material, or the alcoholsor their derivatives and the other addition material may be added at onetime to the mix and the whole worked together.

The alcohol derivatives used are the derivatives of the fatty or atleast oily saturated and unsaturated alcohols, including the poly-hydricalcohols, of the aliphatic series containing 8 or more carbon atoms inthe molecule. The lauryl, cetyl, stearyl, hydroxy-stearyl, oleyl, andricinoleyl alcohols are probably the most satisfactory and the mostcommercially practicable as basic materials because the most readilyavailable as produced from the natural fats and waxes and these alcoholsare sufliciently illustrative of the class. Similar alcohols of lowermolecular weight, for example, having 8 or 10 carbon atoms as well asthose of higher molecular weight such as those which pulverulent orgranular material is to be containing 22 or even 30 carbon atoms can beused advantageously.

The naphthenic=alcohols and their derivatives may also be used asdispersing agents in=accordance with the invention.

The derivatives of the alcohols may be, for example, the ethers with thesame or with lower molecular alcohols, the esters with monoor polybasicacids, or the acid esters of organic or inorganic di-basic acids,preferably neutralized with alkali metals or organic bases.

The ethers may include thosev in which a fatty or oily alcohol iscondensed with the same or another high molecular alcohol or with alower molecular primary alcohol which may be one having as few-as l or 2carbon atoms in the molecule or any of the other primary aliphaticalcohols either saturated or unsaturated and monodior poly-hydric. Thebutyl alcohol and glycerol may be cited as examples of the low molecularalcohols. Phenol and the naphthenic alcohols also may serve as thesecond component of the ether.

The esters may be those formed from a fatty or oily alcohol and amono-basic primary straight chain acid of the aliphatic series havingfrom 1 to 30 carbon atoms in the molecule, as, for example, formic,acetic, acrylic, butyric, caproic, caprylic, capric, lauric, myristic,palmitic, stearic, oleic, linolic, linolenic, ricinoleic, cerotic,melissic, which are sufficiently representative, or a poly-basic organicor inorganic acid, for example, the organic di-basic acids having from 2to carbon atoms in the molecule with or without hydroxyl groups,naphthenic, aromatic and hydro-aromatic dibasic acids of whichillustrative examples are oxalic, malonic, succinic, adipic, tartaric,pyrota'rtaric, pimeric, suberic, azelaic, sebacic, brassylic, boccellic,benzoic, phthalic, hydro-phthalic,

, cyclohexan-diacetic, sulfuric, halogen sulfonic, phosphoric acid andthe like or anhydrides of the same.

The esters of high molecular alcohol with dibasic acids may be eitherdi-substituted esters or acid esters. If acid esters, they may be usedas such, but preferably they are neutralized with alkali metals, alkaliearths or any of the organic bases of which illustrative examples arepiperidine, chinoline, tri-ethylamine, cyclo hexylamine,tri-ethanolamine, tri-propanolamine.

The fatty and oily alcohols and their derivatives not only are excellentdispersing agents and aid in the mixing of the ingredients with rubberor other plastic material, but at least in the case of rubber they alsoimprove the strength and quality of the material. Because of their highboiling points they do not evaporate and are enduring in their effects.

The proportions of alcohol or of the derivatives may vary within widelimits. the total mass of the rubber or of the other plastic materialsthey may be present in as small a proportion as 0.1 or 0.2% of the totalmass and yet have a substantial beneficial effect. On the other handthey may be increased to 3 or 5% and even to a greater extent as, forexample, 10 or 15% of the total weight. Ordinarily the best results areobtained if the proportion does not exceed 5 or perhaps 10%. Probablythe most effective proportions are between 0.1 and 5%.

Apparently the proportion of the alcohol or its derivative to be usedvaries relatively little, if any, with the greater or less amount ofaddition material such as, for example, carbon black, red oxide of ironor other usual coloring and loading materials or liquid or semi-liquidaddition materials.. Obviously the proportion of alcohol or itsderivatives to the addition material may vary within extremely widelimits depending upon the proportion of the material to be added to therubber mix. In usual practice the weight of the alcohol will approximate0.3 to 15% or sometimes of the weight of the addition materials.

While the use of the alcohol or alcohol derivative as a dispersing agentis especially of advantage when adding dusty or granular material, it isalso useful as an aid in distributing liquid or semi-liquid ingredients.This is true both in making rubber mixtures and in the compounding ofother plastic materials.

Example 1.--A rubber composition is prepared containingtogether withparts of the sodium salt of the adipic acid acid ester of oleyl alcoholas a dispersing agent.

under a gradually increasing heat. The product is of a considerablebetter quality than a similar mixture without the addition of the abovenamed dispersing agent.

Example 2.A rubber composition comprises- Parts by weight Latex (75%) 13Chalk 40 Zinc oxide 4 Sulfur 2 Pentamethylendicarbamate of piperidine1.2

together with 2 parts of the sodium salt of the sulfuric acid acid esterof dodecyl alcohol.

Example 3.When rubberizing fabric 1 to 2% of sulfuric acid ester saltsof the type above described are added to-the latex lithopone mixture toimprove the spreading and penetrating properties.

Example 4.-For the purpose of producing carbon-rubber-mixtures of highquality, 24 parts of soot (carbon black) are carefully mixed by grindingor in other suitable manner with 1.2 parts of an ester of fatty alcohol,such for example the cetyl ester of ricinolic acid. The mixture thusobtained is added on the roller to a usual rubber As compared with Themixture may be vulcanized mixture, for example to a mixture consistingof 60 parts of rubber (first latex crepe); 5.25 parts mineral rubber; 6parts of ZnO; 0.6 parts stearic acld;f0.75 parts of diphenylguanidine;2.2 parts of sulfur and after the plasticising the resulting mixture isvulcanized in the usual manner. In the same manner as the cetyl ester ofricinolic acid is also applicable in this batch the dodecyl ester of thebutyric acid.

Example 5.-For the purpose of producing carbon-rubber-mixtures of highquality, 24 parts of soot (carbon black) are carefully mixed by grindingor in other suitable manner with 1.2 parts of an ether of fatty alcohol,such for example, the di-cetyl ether. The mixture thus obtained is addedon the roller to a usual rubber mixture. For example to a mixtureconsisting of 60 parts of rubber (first latex crepe); 5.25 parts mineralrubber; 6 parts of ZnO; 0.6 part stearic acid; 0.75 partdiphenylguanidine; 2.2 parts of sulfur and after the plasticizing theresulting mixture is vulcanized in the usual manner. In the same manneras the di-cetyl ether is also applicable in this batch the pipcridinesalt of the acid sulfuric acid ester of the mono-dodecyl ether ofglycerol.

The term fatty alcohols is used in the claims as including the oilyalcohols.

On account of the distributing and dispersing properties of thesealcohols and their derivatives, the addition materials will be uniformlydispersed in the rubber or other plastic mass and at the same time theunpleasant effect upon the operative of mixing powdery materials withthe mass are in large measure avoided.

It will be understood that the effective dispersion of loading materialsin rubber to be used in thin sheets such as rubber gloves, toy balloonsand the like is of the utmost importance.

The foregoing particular description is illustrative merely and is notintended as defining the limits of the invention.

I claim:

1. A rubber composition containing rubber, carbon black, and a sulfuricacid acid ester of a fatty alcohol neutralized with an alkali or anorganic base.

2. The method of combining insoluble addition substances with rubber orrubber compositions which comprises mixing with the rubber or rubbercompositions the usual compounding ingredients insoluble in the severalingredients of the compositions and a derivative of a high molecularfatty alcohol consisting of an ester of a primary straight chainaliphatic alcohol having 8 to'30 carbon atoms in the'molecule with aprimary straight chain aliphatic acid having 1 to 30 car bon atoms inthe molecule. 1

3. The method of compounding a plastic composition which comprisesmixing with plastic material insoluble pulverulent material and adispersing agent consisting of an ester of a normal primary straightchain aliphatic alcohol having 12 to 18 carbon atoms in the moleculewith an aliphatic acid.

4. The method of compounding a plastic composition which comprisesmixing with plastic material insoluble pulverulent material and adispersing agent consisting of an ester of a normal primary aliphaticalcohol having 12 to 18 carbon atoms in the molecule with a mono-basicprimary straight chain aliphatic acid.

5. The method of combining insoluble addition substances with rubber orrubber-compositions which comprises mixing with the rubber orrubcompounding ingredients and as a dispersing agent therefor an esterof a straight chain aliphatic alcohol having 8 or more carbon atoms inthe molecule with a mono-basic primary straight chain aliphatic acidhaving 1 to 30 carbon atoms in the molecule.

6. The method of combining insoluble addition substance with rubber orrubber-compositions which comprises mixing with the rubber orrubber-compositions usual insoluble pulverulent compounding ingredientsand as a dispersing agent therefor an ester of a straight chainaliphatic alcohol having 8 or more carbon atoms in the molecule with adibasic organic acid having 2 to 20 carbon atoms in the molecule.

7. The method of combining insoluble addition substances with rubber orrubber-compositions which comprises mixing with the rubber orrubber-compositions usual insoluble pulverulent compounding ingredientsand as a dispersing agent therefor an ester of a normal primaryaliphatic alcohol having 12 to 18 carbon atoms in the molecule with amonobasic primary straight chain aliphatic acid having 1 to 30 carbonatoms in the molecule.

8. The method of combining insoluble addition substances with rubber orrubber-compositions which comprises mixing with the rubber orrubber-compositions usual insoluble pulverulent compounding ingredientsand as a dispersing agent therefor an ester of a normal primaryaliphatic alcohol having 12 to 18 carbon atoms in the molecule with adibasic organic acid.

9. The method of combining insoluble addition substances with rubber orrubber-compositions which comprises mixing with the rubber orrubber-compositions usual insoluble pulverulent compounding ingredientsand as a dispersing agent therefor an ester of a normal primaryaliphatic alcohol having 12 to 18 carbon atoms in the molecule with adibasic organic aliphatic acid having 2 to 20 carbon atoms in themolecule.

10. A rubber-composition comprising rubber, usual compoundingingredients insoluble in the several ingredients of the composition andas a dispersing agent an ester of a normal primary straightchainaliphatic alcohol having 12 to 18 carbon atoms in the molecule withan aliphatic acid.

11. A rubber-composition comprising rubber, usual compoundingingredients insoluble in the several ingredients of. the composition andas a dispersing agent an ester of a straight chain aliphatic alcoholhaving 8 or more carbon atoms in the molecule with a mono-basic primarystraight chain aliphatic acid'having 1 to 30 carbon atoms in themolecule.

12. A rubber-composition comprising rubber, usual compoundingingredients insoluble in the several ingredients of the composition andas a chain aliphatic acid having 1 to 30 carbon atoms in the molecule.

14. A rubber-composition comprising rubber, usual compoundingingredients insoluble in the several ingredients of the composition andas a dispersing agent an ester of a normal primary aliphatic alcoholhaving 12 to 18 carbon atoms in the molecule with a dibasic organicacid.

15. A rubber-composition as defined in claim 10 wherein the dispersingagent is of a proportion of 021 to 5% of the composition.

16. A rubber-composition as defined in claim 12 wherein the dispersingagent is of a proportion of 0.1 to 5% of the composltion.

17. A plastic mass comprising, in combination, a caoutchouc basematerial, insoluble pulverulent or granular addition material and, as adispersing agent, a derivative of a high molecular alcohol consisting ofan ester of a primary straight chain aliphatic alcohol having 8 to 30carbon atoms in the molecule with a primary straight chain aliphaticacid having 1 to 30 carbon atoms in the molecule.

18. A plastic mass comprising, in combination, a caoutchouc basematerial, insoluble pulverulent or granular addition material and, as adispersing agent, a derivative of a high molecular alcohol consisting ofan ester of a primary straight chain aliphatic alcohol having 8 to 18carbon atoms in the molecule with a primary straight chain aliphaticacid having 1 to 18 carbon atoms in the molecule.

19. A plastic mass comprising, in combination, a caoutchouc basematerial, insoluble pulverulent or granular addition material and, as adispersing agent, a derivative of a high molecular alcohol consisting ofan ester of a primary straight chain aliphatic alcohol having 8 to 18carbon atoms in the molecule with a dibasic inorganic acid of the groupconsisting of sulfuric acid, halogen acids, halogen sulfonic andphosphoric acids and their anhydrides.

ERNST HELF'I.

